EP0699661A2 - Procédé pour la préparation de sulfonates d'éthers - Google Patents

Procédé pour la préparation de sulfonates d'éthers Download PDF

Info

Publication number: EP0699661A2
Authority: EP; European Patent Office
Prior art keywords: general formula; compound; alkyl; hydrogen; mol
Prior art date: 1994-09-01
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.): Withdrawn

Application number

EP95113205A

Other languages

German (de)

English (en)

Inventor

Klaus Dr. Delpy

Fritz Dr. Engelhardt

Ralf Dr. Zerrer

Dirk Dr. Bühring

Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)

Clariant Produkte Deutschland GmbH

Original Assignee

Hoechst AG

Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)

1994-09-01

Filing date

1995-08-23

Publication date

1996-03-06

1995-08-23 Application filed by Hoechst AG filed Critical Hoechst AG

1996-03-06 Publication of EP0699661A2 publication Critical patent/EP0699661A2/fr

Status Withdrawn legal-status Critical Current

Links

238000000034 method Methods 0.000 title claims description 18
-1 ether sulfonates Chemical class 0.000 title claims description 11
RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title claims description 9
238000002360 preparation method Methods 0.000 title claims description 5
QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 9
125000000217 alkyl group Chemical group 0.000 claims abstract description 9
239000002253 acid Substances 0.000 claims abstract description 8
125000003342 alkenyl group Chemical group 0.000 claims abstract description 5
229910006069 SO3H Inorganic materials 0.000 claims abstract description 4
229910052783 alkali metal Inorganic materials 0.000 claims abstract description 4
150000001340 alkali metals Chemical group 0.000 claims abstract description 4
150000001875 compounds Chemical class 0.000 claims description 29
UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 20
229910052739 hydrogen Inorganic materials 0.000 claims description 17
239000001257 hydrogen Substances 0.000 claims description 17
238000006386 neutralization reaction Methods 0.000 claims description 12
ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 7
239000011734 sodium Substances 0.000 claims description 6
239000010409 thin film Substances 0.000 claims description 6
DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
229910052700 potassium Inorganic materials 0.000 claims description 5
239000011591 potassium Substances 0.000 claims description 5
239000011541 reaction mixture Substances 0.000 claims description 5
229910052708 sodium Inorganic materials 0.000 claims description 5
125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 4
125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
125000006273 (C1-C3) alkyl group Chemical group 0.000 claims description 3
125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 3
125000006552 (C3-C8) cycloalkyl group Chemical group 0.000 claims description 3
125000005915 C6-C14 aryl group Chemical group 0.000 claims description 3
125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 claims description 3
150000002431 hydrogen Chemical class 0.000 claims description 2
150000003839 salts Chemical class 0.000 abstract description 17
125000000753 cycloalkyl group Chemical group 0.000 abstract description 3
125000003118 aryl group Chemical group 0.000 abstract description 2
230000003472 neutralizing effect Effects 0.000 abstract 1
HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
239000000047 product Substances 0.000 description 13
AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 12
238000006243 chemical reaction Methods 0.000 description 12
SUMDYPCJJOFFON-UHFFFAOYSA-N isethionic acid Chemical compound OCCS(O)(=O)=O SUMDYPCJJOFFON-UHFFFAOYSA-N 0.000 description 11
229940098779 methanesulfonic acid Drugs 0.000 description 6
RPACBEVZENYWOL-XFULWGLBSA-M sodium;(2r)-2-[6-(4-chlorophenoxy)hexyl]oxirane-2-carboxylate Chemical compound [Na+].C=1C=C(Cl)C=CC=1OCCCCCC[C@]1(C(=O)[O-])CO1 RPACBEVZENYWOL-XFULWGLBSA-M 0.000 description 6
LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 5
RZXLPPRPEOUENN-UHFFFAOYSA-N Chlorfenson Chemical compound C1=CC(Cl)=CC=C1OS(=O)(=O)C1=CC=C(Cl)C=C1 RZXLPPRPEOUENN-UHFFFAOYSA-N 0.000 description 5
LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
230000001105 regulatory effect Effects 0.000 description 4
150000001298 alcohols Chemical class 0.000 description 3
125000004432 carbon atom Chemical group C* 0.000 description 3
238000006555 catalytic reaction Methods 0.000 description 3
238000004821 distillation Methods 0.000 description 3
238000010626 work up procedure Methods 0.000 description 3
YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
238000004519 manufacturing process Methods 0.000 description 2
230000035484 reaction time Effects 0.000 description 2
238000003756 stirring Methods 0.000 description 2
XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
HHOUUNSSXPYWKJ-UHFFFAOYSA-N 2-(2-hydroxyethoxy)ethanesulfonic acid Chemical compound OCCOCCS(O)(=O)=O HHOUUNSSXPYWKJ-UHFFFAOYSA-N 0.000 description 1
125000006176 2-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 1
125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
150000007513 acids Chemical class 0.000 description 1
125000005210 alkyl ammonium group Chemical group 0.000 description 1
125000003710 aryl alkyl group Chemical group 0.000 description 1
125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
235000010290 biphenyl Nutrition 0.000 description 1
239000004305 biphenyl Substances 0.000 description 1
239000003054 catalyst Substances 0.000 description 1
239000007795 chemical reaction product Substances 0.000 description 1
238000006482 condensation reaction Methods 0.000 description 1
238000001816 cooling Methods 0.000 description 1
125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
238000001704 evaporation Methods 0.000 description 1
230000008020 evaporation Effects 0.000 description 1
125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
229910052736 halogen Inorganic materials 0.000 description 1
150000002367 halogens Chemical class 0.000 description 1
238000010438 heat treatment Methods 0.000 description 1
239000000543 intermediate Substances 0.000 description 1
125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
238000002844 melting Methods 0.000 description 1
230000008018 melting Effects 0.000 description 1
DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
125000001624 naphthyl group Chemical group 0.000 description 1
235000013772 propylene glycol Nutrition 0.000 description 1
238000009419 refurbishment Methods 0.000 description 1
125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
SZINDZNWFLBXKV-UHFFFAOYSA-M sodium;2-(2-hydroxyethoxy)ethanesulfonate Chemical compound [Na+].OCCOCCS([O-])(=O)=O SZINDZNWFLBXKV-UHFFFAOYSA-M 0.000 description 1
239000000126 substance Substances 0.000 description 1
125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
229920002554 vinyl polymer Polymers 0.000 description 1

Classifications

- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/32—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of salts of sulfonic acids

Definitions

the present invention relates to a process for the preparation of high-purity, largely foreign salt-free ether sulfonates by reacting alcohols with hydroxyalkyl sulfonic acid salts under basic catalysis.
Ether sulfonates are important chemical intermediates and are used for a number of industrial applications.
Alkyl groups can be straight-chain or branched and are, for example, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, tert-butyl, n-pentyl, 3-methylbutyl, pentyl-3, n -Hexyl, 2-ethylbutyl or 2-ethylhexyl.
Alkyl R 1 preferably has 1 to 5, particularly preferably 1 to 3, carbon atoms.
Alkyl R2 to R5 or R 2 ' to R 5' preferably has 1 to 3 carbon atoms.
Cycloalkyl is in particular cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl, with cyclopentyl and cyclohexyl being preferred. Cycloalkyl is also understood to mean, for example, dimethylcycloalkyl.
Alkenyl groups can also be straight-chain or branched and correspond, for example, to the alkyl groups mentioned above.
Preferred alkenyl groups have 2 to 5 carbon atoms, with vinyl and allyl being particularly preferred.
Aryl groups are preferably phenyl, naphthyl, biphenyl or fluorenyl, with phenyl being particularly preferred.
Preferred arylalkyl groups are benzyl and phenethyl.
An alkali metal for M is preferably sodium and potassium.
An ammonium group representing M preferably has the formula ⁇ NR6R7R8R9, where R6, R7, R8 and R9 independently of one another represent hydrogen, (C1-C6) alkyl, phenyl, substituted phenyl or halogen. Tetra- (C1-C4) alkylammonium is particularly preferred.
the process according to the invention is a base-catalyzed condensation reaction which is carried out in particular at temperatures of 150 to 250 ° C., particularly preferably 180 ° C. under normal pressure. It is preferred to continuously withdraw the water formed during the reaction by distillation from the reaction mixture.
the reaction times are generally 2 to 10 hours.
the compound of general formula II in an amount of 200 to 700 mol%, the compound of general formula III in an amount of 100 mol% and the compound of general formula IV in an amount of 10 to 20 mol% used.
the compound of the general formula III used in excess is separated off by means of a thin-film evaporator.
a pressure of 10 to 500 mbar and a temperature of 120 to 250 ° C. are preferably maintained.
the compounds of the general formula V can be obtained in a simple manner in that a compound of the general formula I from a previous reaction batch in a manner known to those skilled in the art with a Acid suitable pK s -value was added and the product is isolated.
acids such as sulfuric acid, hydrochloric acid or methanesulfonic acid are suitable.
the compounds of general formula I prepared by the process according to the invention are highly pure and largely free of foreign salt.
largely free of foreign salt means that the foreign salt content of the compounds of the general formula I prepared according to the invention is at most 2% by weight.
the reaction mixture is heated to an internal temperature of 190-190 ° C. with constant stirring.
the jacket temperature of the distillation column is kept at 110-120 ° C.
About 18.0 g of water distill off from the reaction mixture within 3 h.
the alkaline product solution is neutralized by adding approximately 17.0 g (0.1 mol) of 2- (2-hydroxyethoxy) ethanesulfonic acid with constant stirring.
the ether sulfonate is isolated from the glycol-containing product solution by means of thin-layer evaporation.
the jacket heating of the evaporator tube is kept at approx. 200 o C.
the vacuum was regulated to 10 mbar.
the 2- (2-hydroxyethoxy) ethanesulfonic acid sodium salt (Diglykolsulfonklare Na salt) is obtained as a colorless distillation residue having a melting range of 140 -150 o C.
the glycol content is below 1% by weight.
the purity is 98.2% by weight.
the foreign salt content is 0.3% by weight.
the reaction temperature is 210-220 o C, the reaction time 6 h.
the jacket temperature of the heated column is regulated at 160-180 ° C.
neutralization takes place with the sulfonic acid conjugated to the product, and work-up is carried out using a thin-film evaporator as described in Example 1.
the degree of purity is 98% by weight, the foreign salt content is 1.3% by weight.
the reaction temperature is 205-210 o C, the response time 8 h.
the jacket temperature of the column is regulated at 105-110 o C.
the product After neutralization with the sulfonic acid conjugated to the product and working up by means of a thin film evaporator, the product is obtained in a purity of 98.5% by weight, the foreign salt content is 0.6% by weight.
the reaction temperature is 200-210 o C, the response time 6 h.
the jacket temperature of the column is regulated at 160-180 o C.
the product After neutralization with the sulfonic acid conjugated to the product and subsequent work-up using a thin-film evaporator, the product is obtained in a purity of 98.1% by weight and the foreign salt content is 0.2% by weight.

Landscapes

Chemical & Material Sciences (AREA)
Organic Chemistry (AREA)
Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

EP95113205A 1994-09-01 1995-08-23 Procédé pour la préparation de sulfonates d'éthers Withdrawn EP0699661A2 (fr)

Applications Claiming Priority (2)

Application Number	Priority Date	Filing Date	Title
DE4431056A DE4431056A1 (de)	1994-09-01	1994-09-01	Verfahren zur Herstellung von Ethersulfonaten
DE4431056		1994-09-01

Publications (1)

Publication Number	Publication Date
EP0699661A2 true EP0699661A2 (fr)	1996-03-06

Family

ID=6527100

Family Applications (1)

Application Number	Title	Priority Date	Filing Date
EP95113205A Withdrawn EP0699661A2 (fr)	1994-09-01	1995-08-23	Procédé pour la préparation de sulfonates d'éthers

Country Status (5)

Country	Link
US (1)	US5523471A (fr)
EP (1)	EP0699661A2 (fr)
JP (1)	JPH08193060A (fr)
CA (1)	CA2157344A1 (fr)
DE (1)	DE4431056A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
US20040127742A1 (en) *	2002-10-22	2004-07-01	Huntsman Petrochemical Corporation	Alcohol ether sulfonates
BRPI0418061B1 (pt) *	2004-01-20	2019-01-22	Huntsman Spec Chem Corp	uma mistura de éster ânion com propriedades surfactantes para formular produtos de higiene pessoal, e, um produto de higiene pessoal
US7427588B2 (en) *	2007-01-12	2008-09-23	Paul Daniel Berger	Ether sulfonate surfactants and process for making same

Citations (4)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
US2535677A (en)	1947-02-15	1950-12-26	Rohm & Haas	Method for the preparation of ether sulfonates
US4091014A (en)	1976-12-01	1978-05-23	Texaco Development Corporation	Process for making ether sulfonates
US4226807A (en)	1979-06-07	1980-10-07	Texaco Development Corp.	Process for making ether sulfonates
US4465602A (en)	1982-06-11	1984-08-14	Texaco Inc.	Oil recovery method utilizing an alkylarylpolyalkoxyalkylene sulfonate

1994
- 1994-09-01 DE DE4431056A patent/DE4431056A1/de not_active Withdrawn
1995
- 1995-08-23 EP EP95113205A patent/EP0699661A2/fr not_active Withdrawn
- 1995-08-29 US US08/520,712 patent/US5523471A/en not_active Expired - Fee Related
- 1995-08-31 CA CA002157344A patent/CA2157344A1/fr not_active Abandoned
- 1995-08-31 JP JP7223948A patent/JPH08193060A/ja not_active Withdrawn

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
US2535677A (en)	1947-02-15	1950-12-26	Rohm & Haas	Method for the preparation of ether sulfonates
US4091014A (en)	1976-12-01	1978-05-23	Texaco Development Corporation	Process for making ether sulfonates
US4226807A (en)	1979-06-07	1980-10-07	Texaco Development Corp.	Process for making ether sulfonates
US4465602A (en)	1982-06-11	1984-08-14	Texaco Inc.	Oil recovery method utilizing an alkylarylpolyalkoxyalkylene sulfonate

Also Published As

Publication number	Publication date
US5523471A (en)	1996-06-04
JPH08193060A (ja)	1996-07-30
CA2157344A1 (fr)	1996-03-02
DE4431056A1 (de)	1996-03-07

Legal Events

Date	Code	Title	Description
1996-01-19	PUAI	Public reference made under article 153(3) epc to a published international application that has entered the european phase	Free format text: ORIGINAL CODE: 0009012
1996-03-06	AK	Designated contracting states	Kind code of ref document: A2 Designated state(s): AT BE CH DE ES FR GB IT LI NL SE
1998-01-07	RAP1	Party data changed (applicant data changed or rights of an application transferred)	Owner name: CLARIANT GMBH
1999-10-29	STAA	Information on the status of an ep patent application or granted ep patent	Free format text: STATUS: THE APPLICATION HAS BEEN WITHDRAWN
1999-12-15	18W	Application withdrawn	Withdrawal date: 19991020

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